• Membrane Journal
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• v.24 no.6
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• pp.448-452
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• 2014

Nanocomposite membrane to show facilitated olefin transport was prepared for enhanced separation performance. Addtion of halogen molecules into PVP/AgNPs/ TCNQ nanocomposite membrane was expected to further polarize the surface of AgNPs for enhancing the separation performance. The formation of AgNPs and presence of iodine was confirmed by TEM and EDS analysis, respectively. The separation performance for propylene/propane mixture was compared with that of PVP/AgNPs/TCNQ nanocomposite membrane. The long-term stability of membrane was investigated with time.

• Membrane Journal
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• v.15 no.2
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• pp.157-164
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• 2005

In this study, composite hollow fiber membranes were developed for the recovery of olefin monomers in polyolefin industry off-gases. Polyetherimide (PEI) hollow fiber support membranes were fabricated from spinning solutions containing PEI, NMP and polyethylene glycol (PEG). The influence of dope solution and inner coagulant composition on the permeation properties and structure of hollow fiber supports was examined. PDMS was used as a selective layer and coated on PEI hollow fiber support. The thickness of active layer was controlled by changing coating solution concentration. The permeation properties of hollow fiber supports and composite membranes were characterized with a pure gas permeation test. The optimized composite hollow fiber membrane has $10\;{\mu}m$ selective layer and shows excellent separation performance; the ideal selectivity of olefins over nitrogen is in the following order: 1-butylene (6.4) > propylene (17) > ethylene (97), which selectivity data are similar to the intrinsic olefin/nitrogen selectivities of PDMS. This confirms that the new composite hollow fiber membranes suitable for olefin off-gas recovery has developed successfully.

• Membrane Journal
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• v.29 no.2
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• pp.88-95
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• 2019

Hydrocarbons containing carbon double bonds are generally called olefins and it is extensively used in petro-chemical industry as essential base material. Especially, olefins are essential in polymer synthesis and thus the effective separation and purification of olefins from gas mixture are very important and it gives significant positive effect on the future industrial development. In this study, we fabricated polymeric composite membrane based on poly(1-trimethylsilyl-1-propyne) (PTMSP) for propylene/nitrogen separation and enhancement of its separation performance by grafting amphiphilic copolymer. Furthermore, to accelerate facilitated transport for propylene molecules, Ag salt ($AgBF_4$) and ionic liquid ($EMIM-BF_4$) was incorporated to polymer composite membranes. The neat PTMSP membrane exhibited extremely high gas permeance and low gas selectivity due to its high free volume. To address this issue, PTMSP was grafted with poly(oxyethylene glycol methacrylate) (POEM) and poly(ethylene glycol) behenyl ether methacrylate (PEGBEM). Additionally, the additives such as $AgBF_4$ and $EMIM-BF_4$ further increased the propylene permeance, resulting in increment of propylene/nitrogen selectivity.

• Membrane Journal
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• v.29 no.5
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• pp.246-251
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• 2019

Facilitated transport membranes using silver nanoparticles as carriers for olefin/paraffin separation have been interested. $AgBF_4$ has been used as a precursor of silver nanoparticles in previous studies. However, relatively expensive $AgBF_4$ is not suitable for commercialization, and thus, PEBAX-5513/AgNPs (precursor: $AgClO_4$)/7,7,8,8-tetracyanoquinodimethane (TCNQ) composite membranes were prepared using silver nanopaticles with relatively inexpensive $AgClO_4$ precursors. Composite membranes of various compositions were prepared for PEBAX-5513/AgNPs/TCNQ composites, but no separation performance was observed. As a result of FT-IR analysis, it was confirmed that silver nanoparticles were formed in the PEBAX-5513 polymer and the surface of Ag nanoparticles was polarized by TCNQ, but the formed silver nanoparticles were not stabilized. From these results, it was concluded that the anion of the precursor plays an important role in the olefin/paraffin separation.

• Membrane Journal
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• v.25 no.6
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• pp.496-502
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• 2015

Facilitated transport is one of the possible solutions to simultaneously improve permeability and selectivity, which is challenging in conventional polymer-based membranes. Olefin/paraffin separation using facilitated transport membrane has received much attention as an alternative solution to the conventional distillation process. Herein, we report olefin separation composite membranes based on the polymer blends containing $AgBF_4/Al(NO_3)_3$ mixed salts. Free radical polymerization process was used to synthesize an amphiphilic graft copolymer of poly(dimethyl siloxane)-graft- poly(ethylene glycol) methyl ether methacrylate (PDMS-g-POEM). In addition, poly(ethylene oxide) (PEO) was introduced to the PDMS-g-POEM graft copolymer to form polymer blends with various ratios. The propylene/propane mixed-gas selectivity and permeance reached up to 5.6 and 10.05 GPU, respectively, when the PEO loading was 70 wt% in polymer blend. The improvement of olefin separation performance was attributed to the olefin facilitating silver ions as well as the highly permeable blend matrix. The stabilization of silver ions in the composite membrane was achieved through the introduction of $Al(NO_3)_3$ which suppressed the reduction of silver ions to silver particles.

• Membrane Journal
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• v.13 no.4
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• pp.246-256
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• 2003

For the olefin recovery from polyolefin off-gas, the permeation behaviors of olefins and nitrogen were investigated through three kinds of PDMS membranes - cross-linked PDMS membranes, a polysiloxaneimide membrane, and oligo-PDMS modified PDMS membranes. Their pure gas permeabilities were measured as a function of operation temperature(-20 to $50^{\circ}C$) and pressure(1 to 25 atm) with ethylene($C_2\;H_4$), propylene($C_3\;H_6$), butylene($C_4\;H_8$), and nitrogen($N_2$) gases. The permeabilities of olefins and nitrogen highly depended upon the nature of PDMS membranes. Among these membranes, cross-linked PDMS membranes showed stable and high olefin/nitrogen selectivities over a wide operation pressure range and further study in various test conditions. Their permeability of olefin and nitrogen were governed by the condensation temperature(solubility selectivity) and plasticization, not the order of the size(diffusivity selectivity) of gases, which matched well with the general permeation behavior of rubbery polymeric membranes for condensable and non-condensable gases. With increasing feed pressure or decreasing feed temperature, the permeabilities of more condensible olefins increase highly, presumably due to high solubility and plasticization, but that of non-condensible nitrogen decreases slightly and thus, the selectivities of olefin/nitrogen increase highly.

• Membrane Journal
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• v.28 no.4
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• pp.260-264
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• 2018

Poly (ethylene oxide) (PEO)/Ag nanoparticles (AgNPs)(precursor : $AgBF_4$)/p-benzoquinone (p-BQ) composite membrane was prepared for olefin/paraffin separation. As a result, the performance of composite membrane was observed to be maintained at selectivity of 10 and permeance of 15 GPU up to 100 hours. The performance of the membrane was maintained for 100 hours was attributable to that Ag ions could be converted into stable Ag NPs by addition of p-BQ. Furthermore, the surface was partially polarized by the electron acceptor p-BQ, resulting in the formation of olefin carrier. In this study, since the cost of $AgBF_4$ used as a precursor of Ag NPs was relatively higher, $AgNO_3$ was utilized. As a result, it was confirmed that $AgNO_3$ couldn't show the stable formation of nanoparticle, resulting in the poor separation performance.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.69-83
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• 2020

Light olefins are important petrochemicals as well as primary building blocks for various chemical intermediates. As the number of ethane cracking center (ECC) process, in which ethylene accounts for most of the production, has increased in recent years, propylene supply is not catching up with steadily increasing propylene demand. This trend makes the conversion of methanol to olefins to get more industrial importance. The methanol to olefins (MTO) process produces methanol through syngas and obtain olefins such as propylene through methanol. Since the reaction from methanol to olefins provides different product compositions depending on the catalyst used for the reaction, it is important to choose an appropriate separation process for the reaction product with different composition. Four different separation processes are considered for four representative cases of product compositions. The separation processes for the reaction products are evaluated by techno-economic analysis based on the simulation results using Aspen plus. Guidelines are provided for selecting a suitable separation process for each of representative case of product compositions in the MTO process.

• Membrane Journal
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• v.16 no.4
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• pp.294-302
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• 2006

Silver polymer electrolytes are very promising membrane materials for the separation of olefin/paraffn mixtures. Olefin molecules are known to be transported through reversible complex formation with silver ions entrapped iii polymer matrix. However, they have poor long-term stability, which is very important fur the industrial application; the selectivity through the membrane decreases gradually with time mostly due to the reduction of silver ions ($Ag^+$) into silver nanoparticles ($Ag^0$). In this study, the stability of silver polymer electrolyte was investigated for poly(vinyl pyrrolidone) (PVP) and $AgBF_4$ system containing a surfactant, i.e. $C_{18}H_{35}(OCH_2CH_2)_{20}OH$ (Brij98) as a stabilizer. The reduction behavior of silver ions to silver nanoparticles in PVP was also investigated by atomic force microscopy (AFM) and UV-visible spectroscopy. It was found that the growth of silver nanoparticles was slower and selectivity of polymer electrolyte for propylene in propylene/propane was maintained longer time when Brij98 was added as a stabilizer.

• Proceedings of the Membrane Society of Korea Conference
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• 2003.05a
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• pp.7-13
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• 2003